Fluorinated peroxides

ABSTRACT

Novel peroxides having the formula   WHEREIN R is an alkyl or phenylalkyl group, Rf and Rf&#39;&#39; are fluoroperhaloalkyl groups, and M is hydrogen or an alkali metal, are prepared by reacting a peroxide of the formula ROOM with a ketone of the formula RfRf&#39;&#39;C O. The peroxides are useful as free radical initiators for the polymerization of olefins, especially fluoroolefins.

United StatesPatent [191 Anderson et al.

Jan. 7, 1975 FLUORINATED PEROXIDES Inventors: L. Ray Anderson, Morristown, N. l.;

William B. Fox, Alexandria, Va.; Charles V. Hardin, Charlotte, N.C.; Charles T. Ratcliffe, Denville, NJ.

Allied Chemical Corporation, New York, NY.

Filed: Nov. 13, 1972 Appl. No.: 306,072

Assignee:

US. Cl. 260/610 R, 260/92.1 Int. Cl. C07c 73/00 Field of Search 260/610 R, 610 A References Cited UNITED STATES PATENTS 5/1946 Dickey 260/610 12/1948 Dickey 260/6l0 ll/l970 Talbott 260/453 Primary ExaminerBernard Helfin Assistant ExaminerW. B. Lone Attorney, Agent, or FirmRoger H. Criss; Arthur J. Plantamura [57] ABSTRACT Novel peroxides having the formula R: R00 :0M

7 Claims, No Drawings FLUORINATED PEROXIDES This invention provides novel peroxides having the formula lllr ROOCOM wherein R is selected from the group consisting of alkyl groups having one to eight carbon atoms and phenylalkyl groups having the formula wherein each n is independently to2; R, and R, are independently fluoroperhaloalkyl groups having the formula -CF (CFX),,X wherein X is fluorine or chlorine and-n is 0 to 5; and M is hydrogen or an alkali metal.

The peroxides are prepared by reacting a fluoroperhaloketone having'the formula R,R,C=O with a peroxhaving two to five carbon atoms, e.g., tetrafluoroethylene and chlorotrifluoroethylene. Except for the use of a peroxide of this invention as the initiator, the

ide having the formula ROOM, as represented by the following equation wherein R, R R, and M are as defined herein.

The reaction is conveniently carried out at room temperature lf desired, however, the reaction can be carried out at temperatures above or below room temperature, such as, for example, from about -20 to 50C, preferably 0 C to 35C.

The reaction is conveniently carried out under autogenous pressures, but the reaction pressure is not critical. 1

The reaction can be carried out in the absence of other materials, but it is desirable to carry out the reaction in the presence of an inertliquid diluent, preferably a diluent which isa solvent for the product. The product is soluble in polar organic solvents, such as acetonitrile.

The reactants may be added in any order and in any desired proportion. However, his desirable eitherto use a slight excess of the fluoroperhaloketone or to add the fluoroperhaloketone to the reaction mixture until there is no evidence of further reaction. The product can be recovered by removing unreacted reactants and diluent, if any, by evaporation.

Alkyl peroxide reactants suitable for use in this invention have the formula ROOMwherein R is an alkyl group, which may be straight chain or branched, having one to eight carbon atoms, preferably four to eight, and M is hydrogen or an alkali metal. M is preferably hydrogen, lithium, potassium or sodium. Preferably the carbon atom in the alkyl group which is bondedto the oxygen atom is a tertiary carbon atom, as in t-butyl hydroperoxide.

Suitable phenylalkyl peroxide reactants have the formula polymerization is carried out in accordance with conventional methods for polymerizing such olefins in the presence of a catalytic amount of a free radical initiator. Typically such methods comprise polymerizingthe olefin in an aqueous mediumat a temperature of from about 10 to 80 C and a pressure of from 15 to 500 psig. The aqueous medium is usually buffered to a pH between 7 and 11. The peroxides of this invention are employed in a catalytic amount sufficient to' initiate p0 lymerization. Preferably this amount corresponds to a concentration of from'about 0.1% to 2.0 percent by weight in the aqueous medium.

The following examples further illustrate the invention. In each example the reaction was carried out under substantially anhydrous conditions and the product was identified by modern analytical techniques.

a constant pressure of about one. atmosphere. When no further absorption occurred,the reaction mixture was subjected to a vacuum to remove unreacted hexafluoroacetone. The remaining liquid was identified as EXAMPLE 2 Hexafluoroacetone was added to a slurry of' (CH COONa in acetonitrile at 0 C until the (CH3)COONa dissolved to give a clear solution. The

reaction mixture was then stirred at room temperature for 30 minutes. The product was recovered as a residue after the reaction mixture had been subjected to a vacuum at 35 C. By recr-ystallizing the product from methylene chloride, there was obtained a yield of white crystals, melting point 86-87 C, identified as ,(CH COOC(CF ONa.

We claim: l. A peroxide having the formula wherein R is selected from the group consisting of alkyl R; i 2. The peroxide of claim 1 wherein R is an alkyl radi- ROOCLQM I cal having one to eight carbon atoms.

3. The peroxide of claim 2 wherein Rfand R, are trifluoromethyl. I

lithium, sodium or potassium. groups having one to eight carbon atoms and phenylalky] 8'9" havmg the formula radical having the formula 2) I 2)n oHsCOOM (oHai. E

I CH; I wherein each. n s independently O to 2. wherein each n is independently 0 to 2; R, and R, are The Peroxide of Claim 4 wherein and 1 are independently perfluoroalkyl groups having the forfluoromethyl. mula CF (CF )M wherein n is 0 to 5; and M is hydro- 7. The peroxide of claim 6 wherein R is alphacumyl. gen or an alkali metal. g

4. The peroxide of claim 3 wherein M is hydrogen 5. The peroxide of claim 1 wherein R is a phenylalkyl UNITED STATES PATENT AND TRADEMARK OFFICE CERT-EFICATE OF CORRECTIQN PATENT NO. 1 3,859,361

DATED January 7, 1975 INV ENTOMS): L.R. Anderson, W.B. Fox, C.V. Hardin, CH1. Ratcliff e it is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below: v

Column 2, lines 1-5, the formula should read CH l c :H C H (|IOOM .Column 3, line 19, the formula should read CF (Cl=. Column 4, lines 10-14, the formula should read CH Q Signed and Scaled this twent t a [SEAL] yfi D yof Oct0-ber1975 Attest:

RUTH. C. MASON c. MARSHALL DANN Anesrmg Ufjw" (Ommr'ssiuner uj'Parents and Trademarks UNITED STATES PATENT AND TRADEMARK OFFICE r CERTIFICATE OF CORRECTION PATENT NO. 3,859,361

DATED January 7, l975 |N\/ ENTOR( L.R. Anderson, W.B. Fox, c.v. Hardin, C.T. Ratcliffe It is certified that error appears in the above-identified patent and that said Letters Patent Q are hereby corrected as shownbelow:

Column 3, line 19, the formula should read (CF CF Column 4, linel7, "claim 4" should read claim 5 O Signed and Sealed this sixteenth D3) Of March 1976 [SEAL] Attest:

RUTH C. MASON c. MARSHALL DANN Arresting Officer Commissioner ofParenrs and Trademarks 

1. A PEROXIDE HAVING THE FORMULA
 2. The peroxide of claim 1 wherein R is an alkyl radical having one to eight carbon atoms.
 3. The peroxide of claim 2 wherein Rf and Rf'' are trifluoromethyl.
 4. The peroxide of claim 3 wherein M is hydrogen, lithium, sodium or potassium.
 5. The peroxide of claim 1 wherein R is a phenylalkyl radical having the formula
 6. The peroxide of claim 4 wherein Rf and Rf'' are trifluoromethyl.
 7. The peroxide of claim 6 wherein R is alphacumyl. 